Rapid consumption of bromine oxidants in river and estuarine waters

Jaworske, Donald A.; Helz, George R.

doi:10.1021/es00142a008

Cited by 15 publications

(10 citation statements)

References 13 publications

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“…The sequence of events that leads to CHBr 3 production in our experiments are as follows: (1) (Jaworski and Helz 1985). The final hydrolysis is nonenzymatic and spontaneous (Beissner et al 1981) but most likely slower than bromination of DOM.…”

Section: Discussionmentioning

confidence: 89%

“…The chlorination of coastal seawater also produces primarily CHBr 3 , and a sample with high DOM yielded CHCl 3 upon the treatment with a high HOCl concentration (Helz and Hsu 1978; seawater bromide is rapidly oxidized to HOBr by HOCl). Jaworski and Helz (1985) demonstrated that the bromination of DOM from estuarine waters was very rapid (second-order rate constant . 10 7 L mol 21 s 21 ) and that the half-life of HOBr in such waters was , 7 ms. Bromoform was also produced from the addition of bromine water to 0.002% humic acid solution, as were the chlorobromomethanes and trace amounts of CH 2 Br 2 (C.Y.…”

Section: Discussionmentioning

confidence: 99%

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Bromoform production from seawater treated with bromoperoxidase

Lin

Manley

2012

Limnology & Oceanography

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Bromoform (CHBr3; 11–486 fmol L−1 h−1), dibromomethane (CH2Br2; 0–9.4 fmol L−1 h−1), and low amounts of chloride‐substituted chlorobromomethanes were produced from southern California coastal surface seawater upon the addition of algal bromoperoxidase (BrPO) and hydrogen peroxide. Production was greater from water collected near shore than 16 km offshore, presumably reflecting the difference in the reactive dissolved organic matter (DOMreact) concentrations. In the spring, there was an increase in phytoplankton abundance, and CHBr3 production from BrPO incubations was greater, presumably due to increased DOMreact. In the winter, CH2Br2 production was enhanced, although still lower than CHBr3, suggesting a qualitative change in DOM composition due to terrestrial runoff. During the month of the highest precipitation, CHBr3 and CH2Br2 production was enhanced in samples obtained from the mouth of an urban river, suggesting a higher concentration of DOMreact of terrestrial origins. DOM was fractionated by ultrafiltration and subject to the BrPO incubation. The higher molecular weight fractions contained a higher concentration of DOM that was susceptible to BrPO bromination, yielding polybromomethanes. Polybromomethane and iodomethane production associated with phytoplankton blooms results from the reaction between the surrounding DOM, and hypobromous acid (HOBr) and hypoiodous acid released from extracellular (apoplastic) BrPO. The reaction of HOBr and DOM (biological bleaching) could represent a significant DOM degradation pathway. Cell‐free BrPO, derived from dead cells, could remain catalytically active in seawater and produce low amounts of polyhalomethanes prior to biological degradation.

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Section: Discussionmentioning

confidence: 89%

Section: Discussionmentioning

confidence: 99%

Bromoform production from seawater treated with bromoperoxidase

Lin

Manley

2012

Limnology & Oceanography

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“…Jaworske and Helz, 1985). One general uncertainty regarding our model results can be attributed to this reaction.…”

Section: Aqueous Phase Reactions Including Dommentioning

confidence: 85%

“…Implications for the model results: we varied DOM concentrations in the Dead Sea water between 0.0001 g/m 3 and 0.1 g/m 3 and the rate coefficient for the reaction between HOBr and DOM was varied between 10 4 and 10 6 M −1 s −1 (based on Jaworske andHelz, 1985 andPechtl et al, 2007, and references therein). If DOM concentrations exceed 0.01 g/m 3 , HOBr concentrations in the Dead Sea water decrease almost immediately by about two orders of magnitude.…”

Section: Aqueous Phase Reactions Including Dommentioning

confidence: 99%

Modelling chemistry over the Dead Sea: bromine and ozone chemistry

Smoydzin

Glasow

2009

Atmos. Chem. Phys.

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Abstract. Measurements of O 3 and BrO concentrations over the Dead Sea indicate that Ozone Depletion Events (ODEs), widely known to happen in polar regions, are also occuring over the Dead Sea due to the very high bromine content of the Dead Sea water. However, we show that BrO and O 3 levels as they are detected cannot solely be explained by high Br − levels in the Dead Sea water and the release of gas phase halogen species out of sea borne aerosol particles and their conversion to reactive halogen species. It is likely that other sources for reactive halogen compounds are needed to explain the observed concentrations for BrO and O 3 . To explain the chemical mechanism taking place over the Dead Sea leading to BrO levels of several pmol/mol we used the one-dimensional model MISTRA which calculates microphysics, meteorology, gas and aerosol phase chemistry. We performed pseudo Lagrangian studies by letting the model column first move over the desert which surrounds the Dead Sea region and then let it move over the Dead Sea itself. To include an additional source for gas phase halogen compounds, gas exchange between the Dead Sea water and the atmosphere is treated explicitly. Model calculations indicate that this process has to be included to explain the measurements.

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“…The reaction of HOBr and DOM is very rapid, with a half-life of ,7 ms in high-DOM-containing surface waters (400 mmol C L 21 ; Jaworski and Helz 1985). In addition to producing polybromomethanes, diatom-released HOBr will react with reactive components of DOM to form nonvolatile brominated organics, such as haloacetic acids and haloacetonitrils, as they are in water disinfection procedures (Krasner et al 1996).…”

Section: Discussionmentioning

confidence: 99%

Release of reactive bromine and iodine from diatoms and its possible role in halogen transfer in polar and tropical oceans

Hill

Manley

2009

Limnology & Oceanography

101

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An in situ incubation assay measuring the bromination and iodination of phenol red was developed to detect the release of reactive bromine and iodine (primarily hypobromous acid [HOBr] and hypoiodous acid [HOI], respectively) from a putative extracellular bromoperoxidase of marine diatoms. Six of 11 species showed significant release compared to controls. Polar species were particularly active, releasing 0.6-180 fmol HOBr cell 21 h 21 (0.04-1.8 mmol HOBr [mg total chlorophyll] 21 h 21 ; at the seawater bromide concentration, 840 mmol L 21 ) and 1.9-271 fmol HOI cell 21 h 21 (0.02-2.7 mmol HOI [mg total chlorophyll] 21 h 21 , at 100 mmol L 21 iodide). Porosira glacialis consistently showed the highest rates of release. Several temperate diatoms, including Achnanthes cf longipes, known to have a bromide-sensitive peroxidase involved in stalk formation, and warmwater species also showed the ability to release reactive bromine and iodine. This release was influenced by light, temperature, bromide (and iodide) concentration, H 2 O 2 concentration, and pH. The rate of HOBr release by polar diatoms was much greater than bromoform emissions measured by others from laboratory cultures and seaice algae in the field. This indicates that most of the HOBr released may react with dissolved organic matter (DOM) to form nonvolatile bromine organics. Some fraction of diatom-produced HOBr and HOI may also form volatile Br 2 and I 2 , which could transfer to the polar troposphere. The reaction of diatom-released reactive bromine and iodine with seawater DOM may represent the major mechanism in the formation of oceanic polybromo-and polyiodo-methanes.

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Rapid consumption of bromine oxidants in river and estuarine waters

Cited by 15 publications

References 13 publications

Bromoform production from seawater treated with bromoperoxidase

Bromoform production from seawater treated with bromoperoxidase

Modelling chemistry over the Dead Sea: bromine and ozone chemistry

Release of reactive bromine and iodine from diatoms and its possible role in halogen transfer in polar and tropical oceans

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